EP1116773B1 - Composition ignifuge et composition de resine ignifuge - Google Patents

Composition ignifuge et composition de resine ignifuge Download PDF

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Publication number
EP1116773B1
EP1116773B1 EP99938584A EP99938584A EP1116773B1 EP 1116773 B1 EP1116773 B1 EP 1116773B1 EP 99938584 A EP99938584 A EP 99938584A EP 99938584 A EP99938584 A EP 99938584A EP 1116773 B1 EP1116773 B1 EP 1116773B1
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EP
European Patent Office
Prior art keywords
flame
melamine
retardant
flame retardant
resins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99938584A
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German (de)
English (en)
Other versions
EP1116773A4 (fr
EP1116773A1 (fr
Inventor
Yoshifusa Nippon Chem. Ind. Co. Ltd. Hara
Ken Nippon Chem. Ind. Co. Ltd. TAMURA
Takashi Nippon Chem. Ind. Co. Ltd. NISHIMURA
Nobuo Nippon Chem. Ind. Co. Ltd. MATSUMOTO
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Nippon Chemical Industrial Co Ltd
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Nippon Chemical Industrial Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Definitions

  • the present invention relates to a non-halogen base flame retardant composition and a flame-retardant resin composition having smoke suppression properties, emits no irritating odor, and is able to impart superior flame retardancy to various resins while maintaining a inherent mechanical properties of the resins.
  • thermosetting resin for example, a resin composition, in which red phosphorus is blended, (Japanese Patent Publication No. 59-49942), hydrated alumina (Japanese Patent Application Laid-open No. 05-25369), surface treated red phosphorus, hydrated alumina, silica powder (Japanese Application Laid-open No.. 58-198521), and reformed red phosphorus (Japanese Patent Application Laid-open No. 63-156860) as a flame retardant for an epoxy resin, calcium borate and aluminum hydroxide or magnesium hydroxide (Japanese Patent Application Laid-open No.
  • thermoplastic resin flame retardants, for example, magnesium hydroxide (Japanese Patent Application Laid-open No. 54-83952 and Japanese Patent Application Laid-open No. 54-131645) and melamine cyanurate (Japanese Patent Application Laid-open No. 53-31759 and Japanese Patent Application Laid-open No. 54-91558) for a polyamide resin, an organic sulfonate (Japanese Patent Application Laid-open No. 50-98539 and Japanese Patent Application Laid-open No. 50-98540) and sulfimide acid salt (Japanese Paten Publication No.
  • flame retardants for example, magnesium hydroxide (Japanese Patent Application Laid-open No. 54-83952 and Japanese Patent Application Laid-open No. 54-131645) and melamine cyanurate (Japanese Patent Application Laid-open No. 53-31759 and Japanese Patent Application Laid-open No. 54-91558) for a polyamide resin, an organic s
  • red phosphorus is, however, reddish brown, resins are colored by red phosphorus so that coloring is impossible. Furthermore, working environments become worse due to generation of phosphine gas during thermal processing and incineration of resins. In order to suppress this, for example, red phosphorus is covered with a covering agent, but the generation of phosphine gas cannot be completely prevented.
  • Organic phosphorus base flame retardants are particularly notable as non-halogen base flame retardants.
  • the mechanism of its flame retardation is that in high volatile flame retardants, thermally vaporized phosphorus compounds retard combustion of plastics as flame retardants in gas phase by an effect of diluting gaseous oxygen, an effect of cooling combustion system due to vaporization, and an effect of suppressing chemical reactions of combustion, etc.
  • phosphoric acid is produced by thermal cracking due to heating, and this becomes metaphosphoric acid and polymetaphosphoric acid so as to form a nonvolatile phosphoric acid polymer on a surface of a solid phase or fused layer of the burning plastic.
  • the plastic is carbonized by the dehydration reaction of phosphoric acid so as to form a carbonized layer to thereby cut off the access of air, and the supply of external thermal energy so as to retard combustion.
  • Nitrilotris(methylene)phosphonic acid and derivatives thereof are used in various areas as scale inhibitors, anticorrosives, metallic surface treating agents, and chelating agents.
  • Japanese Application Laid-open No. 05-4997 it is disclosed that nitrilotris(methylene)phosphonic acid 6 melamine salt is superior flame-retardant compound.
  • the inventors of the present invention earnestly investigated non-halogen base flame retardants and as a result, noted nitrilotris(methylene)phosphonic acid that has a high phosphorus content, and discovered that a retardant comprising, as effective components, a melamine salt of the aforementioned compound and inorganic retardant could impart superior flame retardancy to various resins without degrading mechanical properties so as to complete the present invention.
  • objects of the present invention are to provide a non-halogen base flame retardant composition which can impart superior flame retardancy to various resins without degrading mechanical properties, generating irritating fume and smoke and to provide a resin composition having superior flame retardancy.
  • the present invention aims to provide a flame retardant composition characterized by containing a nitrilotris-(methylene)phosphonic acid melamine salt represented by the following general formula (1) : (wherein M represents a melamine and n is an integer from 1 to 6), and hydrated metal compound.
  • a nitrilotris-(methylene)phosphonic acid melamine salt represented by the following general formula (1) : (wherein M represents a melamine and n is an integer from 1 to 6), and hydrated metal compound.
  • the present invention also aims to provide a flame-retardant resin composition constitutionally characterized in containing a resin and the aforementioned flame retardant composition.
  • a flame retardant composition according to the present invention is characterized by containing a nitrilotris-(methylene)phosphonic acid melamine salt represented by the following general formula (1): and hydrated metal compound.
  • nitrilotris(methylene)-phosphonic acid melamine salt represented by the general formula (1): nitrilotris(methylene)phosphonic acid ⁇ melamine, nitrilotris(methylene)phosphonic acid ⁇ 2 melamine, nitrilotris(methylene)phosphonic acid ⁇ 3 melamine, nitrilotris(methylene)phosphonic acid ⁇ 4 melamine, nitrilotris(methylene)phosphonic acid ⁇ 5 melamine, nitrilotris(methylene)phosphonic acid ⁇ 6 melamine, etc., are listed. At least one of these compounds can be used.
  • a method for producing the nitrilotris(methylene)-phosphonic acid melamine salt represented by the aforementioned general formula (1) is not specifically limited but conventional method can be used. For example, it may be performed by a method of reacting nitrilotris-(methylene)phosphonic acid represented by the following general formula (2): and a melamoine in water, a mixed solvent of water-acetone, or an aqueous solvent of water-alcohol, etc. at a temperture, genarally, 80 °C or more.
  • the ratio of nitrilotris(methylene)phosphonic acid represented by the general formula (2) and a melamine is usually in the range of 1 to 3 moles of the melamine relative to 1 mole of nitrilotris(methylene)phosphonic acid represented by the general formula (2) and a salt thereof.
  • the amount of the melamine used is appropriately controlled based on the amount of the melamine to be introduced into the objective within the aforementioned range.
  • hydrated metallic compound compounds having a flame retarding function due to endothermic reactions, represented by M m O n ⁇ XH 2 O (M represents a metal, m and n represent an integer of at least 1 determined based on the valence of the metal, and X represents contained water of crystallization), or double salts containing the aforementioned compound, specifically, at least one kind selected from the group consisting of aluminium hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, barium hydroxide, zirconium hydroxide, dawsonite, zinc stannate, zinc borate, aluminum borate, antimony pentaoxide, basic zinc carbonate, cobalt oxide, zirconium oxide, tin oxide, aluminum oxide, titanium oxide, magnesium oxide, calcium silicate, borax, zinc molybdate, zinc phosphate, magnesium phosphate, hydrotalcite, hydrocalumite, kaolin, talc, sericite, pyrophyllite, bentonite, ka
  • Blending ratio of the hydrated metallic compound is usually 1 to 200 parts by weight, preferably 10 to 100 parts by weight relative to 100 parts by weight of nitrilotris(methylene)phosphonic acid melamine salt.
  • a flame-retardant assistant can be concurrently used to enhance the retarding effect.
  • the flame-retardant assistant for example, at least one kind selected from the group consisting of metallic oxides, e.g., antimony trioxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, iron oxide, manganese oxide, aluminum oxide, tin oxide, titanium oxide, and nickel oxide, carbonates, e.g., calcium carbonate and barium carbonate, metaborates, e.g., zinc metaborate and barium metaborate, melamine derivatives, e.g., melamine, melamine cyanurate, methylolmeramine, (iso)cyanuric acid, melam, melem, mellon, succinoguanamine, melamine sulfate, acetoguanamine sulfate, melam sulfate, guanylmelamine sulfate, melamine
  • metallic oxides e.g., antimony
  • the phosphorus base flame retardant for example, at least one kind selected from the group consisting of triethyl phosphate, tricresyl phosphate, triphenyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, diethylenephosphoric acid ethyl ester, dihydroxypropylene-phosphoric acid butyl ester, ethylenephosphoric acid disodium ester, methylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate, ethyl phosphonate, propyl phosphonate, butyl phosphonate, 2-methyl-propyl phosphonate, t-butyl phosphonate, 2,3-dimethylbutyl phosphonate, octyl phosphonate, phenyl phosphonate, dioctylphenyl phosphonate, dimethyl phosphinate, methylethyl phosphinate,
  • Red phosphorus preferably has its surface modified by organic materials or/and inorganic materials, for example, at least one or more of phenol resins, epoxy resins, ethylene-vinyl acetate copolymers, melamine-formaldehyde polycondensates, and hydroxides and oxides of Mg, Ca, Ti, Al, Co and Zr, may be mentioned, although it is not limited to these.
  • organic materials or/and inorganic materials for example, at least one or more of phenol resins, epoxy resins, ethylene-vinyl acetate copolymers, melamine-formaldehyde polycondensates, and hydroxides and oxides of Mg, Ca, Ti, Al, Co and Zr, may be mentioned, although it is not limited to these.
  • Blending ratios of these flame-retardant assistants are usually 0.1 to 10% by weight, preferably are 0.5 to 5% by weight in terms of flame retardant compositions.
  • the flame retardant of the present invention containing nitrilotris(methylene)phosphonic acid melamine salt and hydrated metal compound may preliminary be prepared by a mechanical method imparting a strong sheering force such as wet or dry method so as to achieve a homogeneous mixture having the above ratio of the components, or alternatively, may be formulated separately.
  • the flame retardant composition according to the present invention can impart superior flame retardancy to various resins.
  • thermosetting resins e.g., epoxy resins, phenol resins, polyurethane resins, melamine resins, urea resins, aniline resins, furan resins, alkyd resins, xylene resins, unsaturated polyester resins, and diaryl phthalate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polycarbonates, polyphenylene oxides, polyphenylene ethers, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, polypropylene, polybutadiene, polyacrylonitrile, polystyrene, polymethylmethacrylate, polyethylene oxides, polytetramethylene oxides, thermoplastic polyurethanes, phenoxy resins, polyamides, ethylene/propylene copolymers, ethylene/1-butene copolymers, ethylene/propylene/non-conjugate diene copo
  • thermosetting resins e.g., epoxy resins,
  • thermosetting resin means a synthetic resin being cured to become semipermanently insoluble and infusible, wherein chemical changes due to the action of heat, catalysts, ultraviolet rays, etc., occur to develop cross-linking structure so as to increase molecular weight and to form a three-dimensional network structure.
  • Thermoplastic resin means a resin that exhibits fluidity by heating so that shaping thereof is possible.
  • Blending ratios of the flame retardant compositions into various resins are 1 to 20 parts by weight, preferably 2 to 15 parts by weight in terms of phosphorus relative to 100 parts by weight of the resin. This is due to the fact that when the blending ratio is less than 1 part by weight, flame retarding effects are not sufficiently exhibited and on the other hand, when it is more than 20 parts by weight, it is not preferable since the mechanical properties of molded materials are likely to be degraded even though flame retarding effects are increased.
  • antioxidants of phosphorus base, sulfur base, hindered phenol base, etc. thermal stabilizers, ultraviolet absorbents, lubricants, release agents, dyes, colorants containing pigments, cross-linking agents, softeners, and dispersing agents, as another component blended into resins, is possible.
  • stiffness of the resin can be increased to a great degree by addition of fibrous and/or granular fillers.
  • a filler for example, glass fibers, carbon fibers, metallic fibers, aramid resins, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, calcium silicate, barium sulfate, titanium oxide, fused silica, crystalline silica, magnesia, and aluminum oxide, are listed.
  • the flame retardant composition according to the present invention can be contained in various resins by normal publicly known methods.
  • thermosetting resins the method of concurrently blending the flame retardant composition of the present invention with a thermosetting resin and other additives, and the method of blending a thermosetting resin with a kind of resin components blended beforehand with the flame retardant composition of the present invention, may be mentioned.
  • thermoplastic resins the method of fusing and blending the flame retardant composition of the present invention with an extruder, or the method of uniformly and mechanically blending granular materials all together, and thereafter molding by an extruder concurrently with blending, etc., are listed.
  • the flame retardant composition according to the present invention does not generate a halide gas and irritating odor during combustion while it maintains the inherent mechanical properties of the resin. Therefore, as a very safe plastic material, the flame retardant composition can be used for a broad use of purposes, for example, electric components, e.g., semiconductor sealing materials, laminated sheets, connectors, switches, case members, transformer members, and coil bobbins, building materials, transportation equipment, e.g., automobiles, packages, and housefurnishings.
  • electric components e.g., semiconductor sealing materials, laminated sheets, connectors, switches, case members, transformer members, and coil bobbins
  • building materials e.g., transportation equipment, e.g., automobiles, packages, and housefurnishings.
  • NTP nitrilotris-(methylene)phosphonic acid
  • a resin composition comprising the flame retardant composition of the present invention shows a superior flame retardancy to a resin composition comprising a melamine salt of nitrilotris(methylene)phosphonic acid alone.
  • novolac resin prepared with the ratio of formaldehyde/phenol being 0.9 on a mole basis, in the blending ratios shown in Table 4, and the resulting resin was kneaded by heated roll set at 80 to 90°C for 5 minutes.
  • molded materials having predetermined shapes were formed using a universal press at a molding pressure of 250 kg/cm 2 , for a pressing time of 60 seconds, and at a die temperature of 150°C.
  • Red phosphorus was used after the surface thereof was modified by a phenol resin. (part by weight)
  • Flammability of each sample based on UL94 and generation or no generation of phosphine gas during molding were determined. The results thereof are shown in Table 7. Red phosphorus was used after the surface thereof was modified by a phenol resin. (part by weight) Example Comp.
  • Example 9 10 11 12 8 9 Epoxy resin 100 100 100 100 100 100 100 TMHPA* 80 80 80 80 80 80 80 80 80 80 80 Benzyldimethyl amine 1 1 1 1 1 1 Mg(OH) 2 100 100 100 100 100 Sample A ( P content) 120 (10) Sample B ( P content) 87 (10) Sample C (P content) 72 (10) Sample D ( P content) 63 (10) Hydrated alumina 80 Red phosphorus 10 (Note) TMHPA: tetramethylhexahydrophthalic anhydride U L 9 4 Generation of PH 3 during molding Example 9 V - 0 none Example 10 V - 0 none Example 11 V - 0 none Example 12 V - 0 none Comp. Exam.8 failure none Comp. Exam.9 failure yes
  • Test pieces for a tensile test according to ATSM D-638 were prepared by a 30 mm diameter extruder and injection molding. Then, strength and elongation were measured according to JIS K-7113.
  • Test pieces for evaluation of flame retardancy based on UL94 were prepared in a manner similar to that in the above description, and flammability was measured. The results thereof are shown in Table 9.
  • Red phosphorus was used after the surface thereof was modified by aluminum hydroxide and titanium hydroxide.
  • PP polypropylene resin
  • Table 10 Various additives were added to polypropylene resin (hereafter abbreviated as PP) in the blending ratios as shown in Table 10, and the resulting resin was kneaded by heated roll set at 230°C for 5 minutes. Melt-extrusion was performed at a screw revolution of 87 rpm. Then, test pieces based on UL94 were prepared by injection molding (cylinder temperature: 230°C, die temperature 50°C).
  • Example 22 As tin oxide hydrate, SnO ⁇ H 2 O was used, and as zinc borate, 2ZnO ⁇ 3B 2 O 3 ⁇ 3.5H 2 O was used. (Part by weight) Example Comp. Example 22 23 24 25 10 11 12 13 14 P P resin 100 100 100 100 100 100 100 100 100 100 100 100 100 Sample A (P content) 120 (10) 120 (10) 120 (10) 120 (10) Sample B (P content) 87 (10) 87 (10) Mg(OH) 2 80 80 Hydrated SnO 80 80 Zn-borate 20 20 80 Ammonium polyphosphate 1 Pass or Failure of UL94 v-o v-o v-1 v-o Failure Failure Failure Failure Failure Failure Failure Failure Failure Failure
  • Example 26 27 28 29 15 16 17 18 19 P P o resin 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Sample A (P content) 120 (10) 120 (10) 120 (10) 120 (10) Sample B (P content) 87 (10) 87 (10) Mg(OH) 2 80 80
  • Borax 80 80 hydrotalcite 20 20 20 Melamine polyphosphate 1 Pass or Failure of U L 9 4 V-0 V-0 V-1 V-0 Failure Failure Failure Failure Failure Failure Failure Failure Failure
  • the flame retardant composition according to the present invention can impart superior flame retardancy to various resins while maintaining the inherent mechanical properties of the resins, has a smoke suppression properties, and emits no irritating odor, the composition has great value when used as a non-halogen base flame retardant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

  1. Composition ignifuge, caractérisée par le fait qu'elle contient un sel de mélamine de l'acide nitrilotris(méthylène)phosphonique représenté par la formule (1) :
    Figure 00310001
    (dans laquelle M représente une mélanine et n un nombre entier de 1 à 6), et un composé métallique hydraté.
  2. Composition ignifuge selon la revendication 1, comprenant en outre un agent auxiliaire ignifuge.
  3. Composition ignifuge selon la revendication 2, dans laquelle ledit agent auxiliaire ignifuge est un agent ignifuge à base de phosphore.
  4. Composition ignifuge selon la revendication 2 ou 3, dans laquelle ledit ignifuge à base de phosphore est au moins un type choisi dans le groupe consistant en phosphore rouge, phosphate d'ammonium, polyphosphate d'ammonium, phosphate de mélamine, phosphate de guanylurée, polyphosphate de mélamine et phosphate de guanidine.
  5. Composition de résine ignifuge, comprenant une composition ignifuge selon l'une des revendications 1 à 4.
EP99938584A 1998-08-24 1999-08-23 Composition ignifuge et composition de resine ignifuge Expired - Lifetime EP1116773B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP25177998 1998-08-24
JP25177998 1998-08-24
PCT/JP1999/004525 WO2000011109A1 (fr) 1998-08-24 1999-08-23 Composition ignifuge et composition de resine ignifuge

Publications (3)

Publication Number Publication Date
EP1116773A1 EP1116773A1 (fr) 2001-07-18
EP1116773A4 EP1116773A4 (fr) 2003-03-12
EP1116773B1 true EP1116773B1 (fr) 2003-11-19

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Country Status (4)

Country Link
EP (1) EP1116773B1 (fr)
KR (1) KR100503978B1 (fr)
DE (1) DE69912971T2 (fr)
WO (1) WO2000011109A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3598033B2 (ja) 1999-10-28 2004-12-08 ソニーケミカル株式会社 難燃性接着剤及びこれを用いた回路材
JP2002155210A (ja) * 2000-09-06 2002-05-28 Toyobo Co Ltd 難燃性樹脂組成物及びこれを塗布又は積層した難燃性積層体
TWI292434B (en) 2003-11-07 2008-01-11 Asahi Kasei Chemicals Corp Flame retardant composition
JP4984385B2 (ja) * 2004-10-18 2012-07-25 Ｄｉｃ株式会社 エポキシ樹脂組成物およびその硬化物
KR100893948B1 (ko) 2007-06-25 2009-04-22 리머스(주) 수용성 난연제 조성물, 그 제조방법 및 그 제조방법에 의해제조된 난연제 조성물을 이용한 난연처리방법
US9200122B2 (en) 2007-08-01 2015-12-01 J. M. Huber Corporation Triazine compounds containing phosphorous as flame retardants
DE102007036465A1 (de) 2007-08-01 2009-02-05 Catena Additives Gmbh & Co. Kg Phosphorhaltige Triazin-Verbindungen als Flammschutzmittel
CN102311648B (zh) * 2010-07-02 2016-03-16 重庆市广为道路材料有限公司 一种环保沥青阻燃抑烟改性剂
DE102010035103A1 (de) * 2010-08-23 2012-02-23 Catena Additives Gmbh & Co. Kg Flammschutzmittelzusammensetzungen enthaltend Triazin-interkalierte Metall-Phosphate
JPWO2012165206A1 (ja) * 2011-05-31 2015-02-23 東洋紡株式会社 電気電子部品封止用樹脂組成物、電気電子部品の製造方法および電気電子部品封止体
CN102675372A (zh) * 2012-04-25 2012-09-19 东华大学 一种乙二胺双环四甲叉膦酸三聚氰胺盐化合物及其制备方法
CN104497041A (zh) * 2014-12-09 2015-04-08 东华大学 一种三聚氰胺氨基三亚甲基膦酸盐及其制备方法
CN106046049B (zh) * 2016-07-01 2018-04-27 武汉科技大学 苄胺-n,n-双亚甲基膦酸三聚氰胺盐及其制备方法与应用
CN110922518B (zh) * 2019-11-30 2021-04-23 华东理工大学 一种耐水膨胀型阻燃剂及其制备方法与应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE793200A (fr) * 1971-12-27 1973-06-22 Monsanto Co Compositions ignifuges
JPS5191302A (ja) * 1975-11-28 1976-08-10 Junfunenseimokushitsubannoseizohoho
JP2941078B2 (ja) * 1991-03-30 1999-08-25 城北化学工業株式会社 プラスチック用難燃剤
FR2707308B1 (fr) * 1993-07-09 1995-09-29 Protex Manuf Prod Chimiq Procédé d'ignifugation non permanent de textiles à l'aide de solutions de sels d'acides alkylaminométhylènephosphoniques.
EP0661342B1 (fr) * 1993-12-28 2003-04-02 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Additif pour des résines thermoplastiques et compositions résineuses retardatrices aux flames
JPH07258479A (ja) * 1994-03-18 1995-10-09 Sumitomo Bakelite Co Ltd 難燃性ポリオレフィン系樹脂組成物及びその製造方法

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Publication number Publication date
EP1116773A4 (fr) 2003-03-12
DE69912971T2 (de) 2004-09-02
DE69912971D1 (de) 2003-12-24
KR20010072942A (ko) 2001-07-31
EP1116773A1 (fr) 2001-07-18
WO2000011109A1 (fr) 2000-03-02
KR100503978B1 (ko) 2005-07-27

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